Hydraulic binder



98 x-r Pif* June 261 1955 P. A. J. DOURNUD 2,752,261

. United States Patent: "C6 ma xfs-j, {bwl} 2in1/l 2 Digby" L. "i" if-f cements resides in the immediate production of aluminic wo" k if' and alumina-ferrie gels which considerably impede the Y' if L z 752 261 reaction or the silica with the lime. It is known that in ,Dye 'i df) a complex reactive medium, the reactions tending to first l" 'e' (i, ik HYDRAULIC BINDER 5 take place are the reactions giving off the most heat. As irre 't' a result, when the crushed mixture s ozzola s s fwk" C i A Pierre Andre 'kan Doumaud Toulouse France is brought into the presence of water, the lime first reacts Q o7 `Application December 15, 1951, Serial No. 261,845 With the alumina thus forming alunllno'ferrlc Sels Wlth the alumina and the ferric oxide, and these gels delay the Claims Priority epplieation France December 18 1950 10 chief reaction of the lime with the silica which leads to the formation of the crystallized silicates, conferring its s Claims' (CL 106-117) strength to the cement. The silicates have effectively as a rule the properly of attacking the aluminates, whereas the alumino-ferrc gels are destroyed by the chlorides.

The Present invention relates to a new hydraulic binder It must be noted that some of these salts have already having a mechanical Strength and a Setting Speed equal to been used in addition to the Portland cements, but only or higher than those of Portland cements, but offering very at the time of mixing with water, as catalytic agents for important economical advantages the hydration and not to prevent the formation of alu- It has been known for a long time that the POZZOlallaS, minates or ferro-aluminate gels as these gels are not either natural or artificial, for instance the cellular lavas, formed, or are fon-ned in very small amounts, in the artiwhich contain silica, alumina, ferric oxide and amorphous fida] cements,

lime are Suitable for the Preparation of bindel's- The It must be noted that the addition of sulphates and Romans, for instance, used the pezzolanaserushed and chlorides to the slag cements (without an addition of mixed with fat lime to prepare real cements, the lime addipozzolana) permits also, through the destruction of the tion being necessary to restore tile Stoichionletl'io equi' 25 aluminio gels which tend to be formed, an increase of the librium which is necessary for the crystallization and the Setting speed of such cements, thus reducing in a marked formation of crystals of lime silicates, of lime aluminates manner, the amount of clinker which it is usually neces. and 0f ferro aluminates, aS the natural PS ZlQlanas are sary to add to these cements to gain a satisfactory initial acidic. Since the pozzolana constituents are in the amorstrength,

Phous state, this Probably resulting from the fact that the Concerning the proportions of the various components pozzolana comes from lavas which were in an unbalanced of the cement according to the invention, it must be noted Chemical Stale When Suddenly cooled, this pozzolana, after that they vary according to the raul materials used. In crushing'and mixing wfh lime, and in the Presence 0f particular, as the pozzolanas have, depending upon their Water actS like mii-i colloidal Suspension, the Conlsource, a more or less high silica and alumina content, 'Ponents of which react very Strongly and give l'iSe, Upon 35 they need r more or less large amount of slag to restore setting. te a real Solid solution having a very high nal the crystallization equilibrium. It must be noted that the mechanical Strengthn: tural poizolanas can also be replaced according to the The known peuelanie cements Oler nevertheless a very iu -eutiou l 'powdery ashes resulting from the combustion as a result, they have but a very small initial Strength and 40 ih eleetrie power houses. In all the eases, the cement can reach a Sulhcient Strength only aftel' about 23 daysaccording lo the invention is constituted by a mixture of .114ktaiuatifactominitistfengls, it becomes therenatural or artificial pozzolanas with granulated blast furfore necessary to reduce`i`n the` pozzolanic cements the nace slag and dus not need any heating for its prepara. amount of pozzolana to about 25 to 30% and to use, in tion, the enly necessary fuel being the fuel used to dry the mixing, 70 to 75% of artificial clinker. In view of the 45 the raw m `tel-als, thus giving, in relation to the articial cost, this is of little interest, the onlyadvantage of these cements, a coal saving ranging up to 250 kg. per ton of cements consisting in their improved resistance to some cement produced. Water, selenitic vater Particularlyi As an example, a method for the preparation of the i The object of the present invention is to produce pozzocement according to the invention is described hereafter, .lanie cements offering all illitialnstrength similar to the the mechanical properties of the cement as compared strength of artificial Portlauceliieiimmd "high with the properties of the chief types of cements known initial strength cements, but maintaining the benet of being llustrared in the annexed drawing.

the low Cost 0f the poilolanie cements iliade Without the In the drawing the curve l shows, as a function of the addition of a large amount of artificial cement. time, the jim-ease in strength of the usual pozzolanic The cement, according to the invention, is characterized cement, om taining 30% of pozzolana.and 70% of Port` in that it is made with a mixture opgzolana and of blast landcmem, "elghal it is only after 28 days that ,EQeSISJEiJmEL in the Propomti'ef40` such''cemie'r-lt will reach the strength of about 270 kg., a establish between components an equilrbrium whleh strength which is reached after 7 days by the usuel Portallows the formation of a crystallized system. land cement (curve 2) and in 2 days by a Portland As the last furnace sla is basics it Willltilre the cement with a high initial strength" (curve 4l, produced l t content an a dou e urnln e cement accor mg furnace slag resulting from the sudden cooling in water to ,he invemgn (curve 3) an ample of which is given 0f 'he melting slag' @meins a diceleium silicate which hereafter. makes possible an initial strength slightly has the property of losing instanteueeusly in the pteseuce 65 smaller than the strength of the Portland cement with a cf Water' a lime molecule thus Starting the reaction with high initial strength. and a final strength slightly higher.

the siliee- A As above indicated, the first problem lo be solved in According to au other lmptlltant feature of the inven' the preparation of a pozzolanic cement consists in obtaintion, this Cement Contains also Calcium Sulphate and/or a ing an alkaline correction to balance the acidity of the chloride (specially Calcium Chloride) and preferably bari- 7'0 pozzolana and lo reach the equilibrium conditions which um chloride. The inventor has indeed discovered that the are necessary for crystallization. As above indicated, most important cause of the slow setting of the pozzolanic h this correction, according to the invention, is carried on,

Serious drawback because their Setting is very Slow and, o1 coals su: n as the coals used to feed the boiler furnaces not by an addition of lime or of Portland b the addition of a mniairm material easy to find in large quantities and at a low price. The two chief components of the cement according to the invention are dried and ground together to the same neness as a Portland cement having a high initial strength.

The second problem c insists, upon the addition of the tempering water, in bringing quickly in solution the silica and the alumina. In order to facilitate the operation, it is proposed, according to the invention, to add to the ground mixture an alkaline component, since the silica and alumina are soluble in alkalis. This addition of alkali is made in the form of an alkaline salt, prefferably sulphate of ammonia. The ammonia is shifted by the lime which brings into solution the silica and the alumina by preventing the formation of protective layers by the aluminates and promoting the reaction in sequence of the silicaand-the lime. One knows that, as the lime p'sses'into solution, it coalesces with the silica and the solution is no longer saturated with lime, thus allowing a new amount of lime to pass into solution and to coalesce with the silica, and so on, this sequence lasting possibly until the total amount of lime has entered into combination.

A third problem, which has been set forth above, consists in preventing the formation of aluminc and ferro aluminc gels. The problem is solved by the addition, during crushing, or in the tempering water, 1 to 3% by weight of calcium sulphate, which attacks the aluminc gels, and 1 to 3% by weight of chlorides, e. g. calcium chloride, which attack the aluminoferritic gels. The addition of said salts, which arc hygroscopic (the chlorides particularly) may result in making the cement sensitive to the moisture. Advantageously, therefore, the calcium chloride is replaced by barium chloride, which is not hygroscopic, and seems to have an even more elective action, on account of its reaction with the calcium sulphate. Indeed, with the addition of barium chloride in a solution of calcium sulphate, a double decomposition takes place, according to the reaction:

CaSO4+ BaClz.2N2O- BaSOl-I-CaClz-l-ZHzO The result is that, upon tempering with water, a calcium chloride in the nascent state is formed which has a greater action on the gels to be destroyed. It is nevertireless necessary to proportion the addition of barium chloride so that part'of the calcium sulphate is left unattacked and will act on the lime to dissolve it and promote the reaction in sequence of silica-lime as abovei indicated.

According to another characteristic feature of the invention, the starting of the reaction is produced by adding, in a rather small proportion, tricalcium-silicate, in addition to the tricalcium silicate already contained in the granulated slag, for instance in the form of about 5 to of Portland cement or of an alkaline salt, a sodium sulphate or silicate for instance.

Finally, as the speed of formation of the crystallized system depends in part on the temperature (one knows that this crystallization is for instance, much faster when itis adiabatic without yielding to the ambient medium the heat given off by the reaction), on'e adds tothe mixture -,ton, for instance..itt.'1n.lmo ugt of 3%, thus giving rise t5 a further liberation of heath'o? calories per kilogram of cement.

As an example, a cement according to the invention shall be described. It is made with a pozzolana constituted by volcanic scorias with the following composition:

Percent SiO: 46 A120: l5 Feo: Y- 12 4 CaO 9 MgO 4 K2O 6 NaO and with a granulated slag having the following composition:

Percent SiOz 30 Al203 1l CaO 5l Fe 0.3 Mn 0.4 S 3 With these two chief components, a cement was made, including:

The whole was mixed, dried and crushed, to a degree of neness giving a residue of 4% on a screen of 4900 meshes.

This cement has shown in tests the following resistances, as shown by the curve 3 of the annexed drawing:

KgJcm? After 48 hours 214 After 7 days 3l5 After 28 days 365 After days 450 showing thereby an initial resistance very close to the initial resistance of Portland cement having a high initial resistance (curve 4) and a higher final resistance after 90 days.

With the addition to the above mixture of 0.5% of ammonium sulphate the tests have shown a strength illustrated by the curve 5:

Kg. 'cm.2 After 48 hours 300 After 7 days 400 After 28 days 450 this strength is very distinctly higher than the strength of a Portland cement having been baked twice (curve 4), and with a much lower cost.

The cement according to the invention can be used for very many purposes, in particular for the making of a cellular concrete, for the cold manufacture of tiles and bricks and can also be used, with the addition of a metallic powder or of any other means to produce air-er trainment, concretes or aerated concretes.

What I claim is:

l. Cement constituted by a mixture of:

56% in weight of blast furnace granulated slag comprising 30% of SiOz and 5l% of CaO 30% of pozzolana comprising 46% of SiO: and 9% of CaO 7% Portland cement 3% lime stone 3% calcium sulphate 1% barium chloride,

crushed to a degree of iineness giving an oversize of 4% on a screen having 4900 meshes.

2. Cement according to the claim l with the addition of 0.5% of sulphate of ammonia.

3. A water setting cement composition formed by a mixture of pozzolana and of basic water granulated blast furnace slag wherein the proportions of pozzolana and of blast furnace slag are selected to neutralize the acidity 0f pozzolana, said mixture further comprising calcium sulphate and calcium chloride each in a proportion from of 5% to 10% ofthe total weight of the mixture, where- 1% to 3% to prevent the formation of aluminio and by the proportiors of pozzolana and blast furnace slag ferro-aluminic gels respectively. are selected to neutralize the acidity of pozzolana, the mix- 4. A water setting cement composition formed by a ture further comprising calcium sulphate and barium chlomixture of pozzolana and of basic water granulated blast 6 ride each in the proportion from 1% to 3% of the total 1% to 3% of the totai weight of the mixture, whereby 10 of about 3% of the total weight of the mixture, wheremixture of pozzolana and of basic water granulated blast 15 total weight of the mixture.

of blast furnace slag are selected to neutralize the acidity References Cited in the le of this patent of pozzolana, said mixture further comprising calcium UNITED STATES PATENTS sulphate and barium chloride each in a proportion from 270 608 R Lb I 16 1883 1% to 3% of the total weight of the mixture, whereby 20 1 033'984 B --Jlln' 30 1912 calcium chloride in a nascent state is formed in presence 1'465'115 egg "A y 14' 193 of water allowing the aluminio and ferroaluminic gels '1'627'237 Fry gg' 19?7 to be destroyed, and ammonium sulphate in a proportion l udmg ay 3' of about 05%. .831,702 Cdl'e NOV. 10, 1931 6. A water setting cement composition formed by a 25 1'912'883 Bhnk June 5 1933 mixture of pozzolana, of basic water granulated blast 11997382 Wndecker APF 15- 1935 l furnace slag and of trcalcium silicate in the proportion 2,115,459 Kwa May 3 1938 of 5% to 10% of the total weight of the mixture, where- 2,125,520 PFkCl al- Allg- 2. 1938 by the proportions of pozzolana and blast furnace slag 2,302,988 Witty Nov. 24, 1942 are selected to neutralize the acidity of pozzolana, the mix- 30 2,446,990 Scizuetz Aug. 10, 1948 ture further comprising calcium sulphate and barium chloride each in the proportion from 1% to 3% of the FOREIGN PATENTS total weight of the mixture. 12,621 Great Britain of 1906 7. A water setting cement composition formed by a 467 Great Britain of 1908 mixture of pozzolana, of basic water granulated blast 3 5 546,629 Great Britain Ju1y22, 1942 furnace slag and of Portland cement in the proportion 

3. A WATER SETTING CEMENT COMPOSITION FORMED BY A MIXTURE OF POZZOLANA AND OF BASIC WATER GRANULATED BLAST FURNACE SLAG WHEREIN THE PROPORTIONS OF POZZOLANA AND OF BLAST FURNACE SLAGE ARE SELECTED TO NEUTRALIZE THE ACIDITY OF POZZOLANA, SAID MIXTURE FURTHER COMPRISING CALCIUM SULPHATE AND CALCIUM CHLORIDE EACH IN A PROPORTION FROM 1% TO 3% TO PREVENT THE FORMATION OF ALUMINIC AND FERRO-ALUMINIC GELS RESPECTIVELY. 